Process of treating decolorizing and clarifying hydrous magnesium silicates



Nov. 24, 1925. 1,562,868

M. L. CHAPPELL coLoRlzINe AND CLARIFYING HYDRous MAGNBSIUM sILIcATEs PROCESS 0F TREATING DE Filed 001,. 15. 1924 Patented Nov.. 24, 1925.

UNITED STATES 1,562,868 PATENT OFFICE.

MARVIN L. CHAPPELL, OF INGLEWOOD, CALIFORNIA, ASSIGNOR TO STANDARD OIL COMPANY, OF SAN FRANCISCO, CALIFORNIA,

A CORPORATION OF CALIFORNIA.

PROCESS OF TREATING DECOLOBIZING AND CLABIFY ING HYDBOUS MAGNESIUM BILICATES.

Application led October 15, 1924. Serial No. 743,746.

To aU whom z't may concern.'

Be it known that I, MARVIN L. CHArrnnL,

a citizen of the United States, residing at Inglewood, in the county of Los Angeles and 6 State of California, have invented a new and useful Process of Treating Decolorizing and Clarifying Hydrous Magnesium Sillcates, of which the following 1s a specification.

This invention relates to a method for treating agents suitable for clarifying and decolorizing petroleum oils and refers particularly to a process of revivifying a clarifying and decolorizing hydrous magnesium silicate.

Hitherto certain forms of hydrous ma esium silicates have been employed as clarlfying and decolorizing agents in the treatment of petroleum oils. Certain of these hydrous magnesium silicates have been found to possess a clarifying and decolorizing efficiency of from two to as hi h as four times that of Florida fullers eart such material has been employed in the clari ing or decolorizing of petroleum oils, it is oun'd that the present known methods of revivifying other clarifying and decolorizing agents are ineffective to completely restore the original active clarifying and decolorizing powers of the agent.

I have discovered a process by which clarifying and decolorizing agents of the hydrous magnesium silicate c ass may be treated to obtain not only a com lete recovery of the original clarifying and decolorizing roperties of the agent, but also an additlonal clarifying and decolorizing eiiiciency of from two to as high as five per cent or more, thereby producing an agent having a clarifying and decolorizing efficiency ranging from 102 to as high as 105 per cent as compared with the agent before used.

More specifically, I have found that clarifying and decolorizing a ents of the hydrous magnesium silicate c ass can be most effectively revivified by the use of a color solvent containing sulfuric acid, provided that the quantity of sulfuric acid employed upon the agent is within certain limits hereinafter set forth. Y

The clarifying and decolorizing agents to be treated by this process belong to that class of hydrous ma esium silicates having high natural clari ng and decolorizing properties, such as materials belonging to the serpentine and talc division as classified in Danas text-book of Mineralogy, 1912 edition, published b John Wiley & Sons. Such natural clarig'ing and decolorizing agents of the serpentine and talc division are principally silicates thou h they may contain lesser quantities of aluminum and other minerals.

As a specific example the following is an analysis of a clarif ing and decolorizing agent having a hig natural decolorizing property with reference to etroleum oils and which ma be revivifie for reuse by the process of t is invention and which after revivification will possess even a greater clarifying and deco orizing roperty than the original natural agent. his particular clarif ng and decolorizinga ent was obtaineV from the Amargosa V ley, Nevada:

g Per cent. S10 55.40 M 23.30 A120, 4.97 Free H2O 9.40 Combined H2O and vol. matter 6.93

Such clarifying and decolorizing agents when employed to clarify and improve the color of petroleum oil in accordance with the processes described in U. S. Patents Num er 1,404.374 and 1,404,375, anted to Marvin L. Chappell and Merle Moore, or employed in any other preferred manner for the decolorizing and clarifying of petroleum oils may be revivied by the process of this invention.

In the process I employ an organic solvent containing sulfuric acid in solution. Such organic solvent preferably contains a ketone such as acetone, methyl-ethyl ketone, etllyl ketone' or ethyl-propyl-ketone of which acetone for commerelal reasons is preferred. The organic solvent also preferablyincludes alcohol of which methyl, ethyl, propyl or butyl may be used. To the color solvent is 1preferably added a solvent suitable to disso ve such mineral oil asl may be left in the clarifying and ,decolorizing agent. Such oil solvent may be carbon derived from petroleum oil or an aromatic hydrocarbon such as benzol, toluol, xylol or mixtures of any such or like mlneral solvents.

In order to illustrate a speclfie example a. hydroof magnesium al- 4 of a process cinbod ing the invention, reference is made to t e accompanying drawings which illustrate diagrammatically an apparatus in which the process may be conducted, it being understood that the invention is :for the method and not limited to the use of any particular apparatus or to the s eciiic example of the method given for il ustration.

Referrin to the drawings, 2 indicates a tank provi ed with a top with a manhole 3 into which a conveyor 4 is ,positioned to empty, said conveyor leading from the source of s ent a t, not shown. To the bottom of t e tan 2 is connected a pipe 5 which is provided with suitable valves 6 and 7 and leads to the outlet end of a pump 8. To the outlet end of the pump 8 is connected a pipe 9 controlled b valves 10 and 11 terminating in the ta 2 in the swing pipe section 12. Thus the tank 2 is provided with a circulating system comprisin the swing pipe section 12, pipe 9, 4pump and pipe 5.

eading from the inlet side of the pump 8 is a line 13 which is controlled by valves 14 and 15 and communicates with a solvent acid solution tank 16 at' its. bottom. Said tank 16 is provided with a suitable inlet pipe 17 contro led by a valve 18 such inlet pipe 17 leads to a source of said solvent solution (not shown).

The bottom of tank 2 is connected by a pipe 19 and controlled by a valve 20 which is connected to the inlet end of a pump 21 the outlet end of the ump being connected to a lter 22. The 'i ter 22 may be of any well-known type either operated under vacuum or pressure and is provided-witli a pipe 23 controlled b a valve 24 which pipe is arranged to con uct filtered liquid to a used solvent solution tank 25. A pipe 26 controlled by a valve 27 connects the outlet end of the pump 8 to the to of said tank 25. Said tank 25 is provid with a line 28 connected to an'inlet end of a pump 29, the discharge end of the ump connecting through a line 30 control ed by a valve 31 with a still 32.

The still 32 may be of any preferred construction, for similar vdistillation operations, the still 32 preferably being provided with a draw-otf pi 38 which is shown including a pump 34 with valves 85 and 36 at oppose sides of the pump. A vapor line 37 leads from the top of the still 32 to a condenser 38. Said condenser 38 discharges through a line 39 controlled by a valve 40 into the top of the acid solution tank 16.

An evaporatin tank 41 is positioned under the lter 22 an provided with a man-hole 42 through which the agent may be introduced from the filter 22. 'A suitable steam coil 43 is provided within the evaporating tank 41. 44 indicates a vapor line which leads from the evaporating tank 41 to a condenser 45. Said condenser 45 discharges through a line 46 into the tank 25. At the bottom of the evaporating tank 41 is provided a man-hole 47 and a conveyor 48 is positioned under the man-hole and is adapted to carry awa the finished agent.

In con uctng the rocess of a solvent mixture containing vsul uric acid in solution is introduced into the tank 16 through the pipe I7. As an example of a suitable solvent mixture said mixture may contain ten parts by volume of acetone, thirt parts by volume of denatured ethyl alcoho and sixty parts by volume of gasoline. Such a SQL vent constitutes both an oil and color solvent. To this mixture is added from one to five volumes of 41.4 Baume sulfuric acid it bein understood that the strength of acid ad ed may be varied somewhat without destroying the advantages to be derived from the invention and will depend somewhat upon the strength of denatured alcohol em loyed. v

e desired quantity of acid solvent contained in tank 16 is then introduced into the treating tank 2 passing through pi 16 into suction side of pump 8 which discharges into pipe 5 and passes into the bottom of the treating tank 2, valves 15, 14, 7 and 6 being open and valves 20, 21, 10 and 11 bein c osed. As soon as suicient quantity of aci solvent has been introduced into the treating tank 2 valves 15 and 14 are closed and valves 10 and 11 are opened which permit the acid solvent to circulate 'ng through the swing pipe 12 throng pipe 9 into suction end of pump 8 which ischarges into the bottom of treating tank 2 through `pipe 5 thus producin an agitation therein.

The desire quantity of s nt clarifying and decolorizing agent whic is understood to belong to the hydrous magnesium silicate class, is then introduced into the treating tank 2 b operation of the conveyor; the material ing introduced through man-hole 3. The relative pro ortions'of acid solvent and clarifying and ecolorizing agent may be widely varied, however in practice it is found convenient to employ six pounds of agent for every gallon of solvent during a sin le wash.

irculatory agitation of the acid solvent is maintained in the treating tank 2 during introduction of the s ent clarifying and decolorizing agent an maintained until the solution action is complete after which pump 8 is stopped and the mixture is allowedV to stand until the washed agent has settled to the bottom of the treating tank 2.

As soon as substantially all of the washed agent has settled to the bottom of the treating tank 2, swin pipe 12 is adjusted so that most of the us acid solvent mav be separated from the washed agent. This is accomplished by operating pump 8, valves 7 and 6 being cosed and valve 27 being open. Thus most of theY settled acid solution is separated from the washed agent and discharged through pipe 26 into the spent solvent receiving tank 25. i

In a likemanner as before the said agent is again given two, three or more washes with acid solvent until it is substantially free of impurities.

During the subsequent washes of the clay it is not generally necessary to employ acid in the solvent. Apparently the initial treatment of the agent with the acid solvent is sulicient to enable the solvent without the acid to completely remove the-coloring matter from the agent.

As soon as the washed agent contained in the treating tank 2 is suliiciently free of impurities the agent is conducted to the lil-ter 22 which separates more of the used solvent from the washed agent by a pressing operation. The washed, pressed agent still containing a small percentage of solvent vpasses from filter press 32 into the evaporator 41 which is heated' by steam passing through steam coils 43. In the evaporator 41 the washed agent is completely free of the re maining solvent which is there converted into a vapor and passestljirough vapor line 44 and is condensed in cooling coil 45 being collected in tank 25.

As soon as the washed and treated a ent is free of, the solvent, it is conducts to storage by conveyor 48 and* can be used agiain to clarify and decolorize petroleum oi The used solvent contained in tank 25 is recovered for reuse by a distillation o eration. Pump 25 discharges the used so vent into the still 32 wherein the solvent is vaporized, asses through vapor line 37, is condensed) in cooling coil 39, and passes finally intoV the solvent tank 16 for reuse. After the distillation-operation of the used solvent there remains in the bottom of the -still 32 the petroleum oil which was retained by the agent in the clari ing and decolorizing operation, the coloring matter which was extracted and a small percentage of mineral solvents extracted during the re vivifying operation.

impoitant feature of the invention is the utilizationof an acid solvent solution containing just the requisite sulfuric acid to effect a complete revivifcation of the original active properties of the decolorizing agent. In fact by use of the proper quantity of the sulfuric acid in the acid solvent I am enabled to produce a revivified agent containing a greater cliiciency than the original clay.

For the pur ose of illustration, the accompanying ta ulation shows the relative eliiciency of the revivified clarifying and v eiliciency of reviviliediclarifying and decolorizing agent. the original activcpurities of the agent being considered 100%.

i n c H180; Emcency Per cent Per cent Per een! 1 l M 1m 2 1 100 5 2% 105 7 3% 90 10 60 It will be observed that with quantities of sulfuric acid less than 7% by weight (corresponding to less than 5% by volume) the revivified agent possesses at least as high a decolorizing eliiciency as the natural agent, and by selecting asolvent of the proper'acid strength the revivified agent can be made as high as 5% more eliicient that the natural agent.

`It is understood that various modifications and changes in the process ma be made without de arting from the spirit of` this invention. is invention is not limited to the specific rocess described, but is of the. scope set fort in the following claims.

I claim:

1. The dprocess of treating spent decolorizing an clari ing agent containing .as the basic ingre ient hydrous magnesium silicate which comprises contacting the silicate with a color solvent containing the requisite sulfuric acid to restore at `least the ori inal decolorizing and clarifying powers of t e silicate. 4

V2. The rocess of treatingspent clarifying and deco orizin agent containing as the basic ingredient ydrous magnesium silicate, which comprises washinv the spent silicate with a color solvent containing sulfuric acid.

3. The process of treating a spent clarifying and decolorizing agent containing as the basic ingredient hydrous magnesium silicate' which comprises washing said spent silicate with a color solvent containing less than .3l/2% by weight of sulfuric acid.

4. The process of revivifying a spent clarifying and decolorizing agent containingr as the basic ingredient hydrous magnesium silicate, which comprises washing such sili cate with a color solvent containing a ketone and sulfuric acid.

5. The process of treating a spent clarifying and decolorizing agent containing as the basic ingredient hydrous magnesium 1 acid.

silicate which comprises washing the spent silicate with n colorsolvent containing sulfurie acid. A

6. The roce of revivifying spent clmfi-A `in an decolorizing agent contini asA t e -sie ingredient hydrous magnesium 4silicate wh'ch includes washing the spent silicate wit a. solvent containing a ketone and less'than S15/2% by weight of sulfuric 7. The recess of revivifying spent clarifyng an 'decokJl-izing agent containing as the basic ingreient hydrous magnesium silicate which comprises washing the spent 15 silicate with a solvent containing the 'requi- 8. The recess of revvifyi'ng spent clar- I :in decolorizing agent containing as the basic ingredient hydrous magnesium silite which com' rises treating smdspent. silicate with' a' so vent. comprising acetone 'and alcohol and the requisite sulfuric acid to' restore at least the ngtuml clarifying and (lecolorizing properties of the silicate.

Signed at LosV Angeles, California, this 19th day of September, 1924.

i MARVIN L. CHAPPELL.

silicate which comprises Washing thc spent silicate with a color solvent containing sulfuric acid.

6. The recess of revivifyingg,r spent clarifyin an decolorizing agent containing as the asie ingredient hydrous magneslum silicate which includes washing the spent silicate with n. solvent containing n ketone and less than 31/98 by weight of sulfuric acid.

7. The recess of l'cvivifying spent clarifying an decolorizing;r agent containing as the basic ingredient hydrous magnesium silicate which comprises washing the spent silicate with a solvent containing the requi- Pam. Ne. 1,562,868.

site sulfuric acid to restore the silicate tn a clarifging and decolorizing efficiency in excess o its natural eiiiciency.

8. The process of revivifying spent clarifying and decolorizing ugent containing as the basic ingredient hydrous magnesium silicate which comprises treating.'` said spent silicate with a solvent comprising acetone and alcohol and the requisite sulfuric acid to restore at least the natural clarifying and (.lccolorizing properties of thc silicate.

Signed at Los Angeles, California, this 19th day of September, 1924.

`MARVIN L. CHAPPELL.

Certificate of Correction. i

Granted November 24, 1925, to

MARVIN L. CHAPPELL. It is hereby certified that error appears in the printed specification of the abovenumbered patent requiring correction as follows: Page word color insert the words and m2,' and that the said 4 line 2, claim 5, after the Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Oice.

Signed and sealed this 4th day of October, A. D. 1927.

M. J. MOORE, Acting Ummm'saoner of Patents.

Certificate of Correction. I Patent No. 1,562,868. Granted November 24, 1925, to MARVIN L. CHAPPELL.

It is hereby certified that error appears in the printed specification of the abovenumbered patent requiring correction as follows: Page 4 line 2, claim 5, after the word oolor insert the words and 012; and that the said Letters Patent should be read with this correction therein that the same may conform to the reoord of the oase in the Patent Office.

Signed and sealed this 4th day o October, A. D. 1927.

[SEAL] M. J. MOORE,

Acting 'owwnssioner of Patents. 

